Ziegler-natta catalyst for olefin polymerization, method for preparing polyolefin, and polyolefin resin

Abstract

Provided are a Ziegler-Natta catalyst for olefin polymerization, a method for preparing polyolefin, and a polyolefin resin. Specifically, provided are a Ziegler-Natta catalyst for olefin polymerization, a method for preparing polyolefin by using the catalyst, and a polyolefin resin prepared by using same, the Ziegler-Natta catalyst for olefin polymerization comprising: a Ziegler-Natta pro-catalyst for olefin polymerization comprising a titanium compound represented by chemical formula 1, a magnesium compound represented by chemical formula 2, and an internal electron donor; an organoaluminum compound represented by chemical formula 7; and an external electron donor represented by chemical formula 3, wherein the internal electron donor is a mixture of a first internal electron donor selected from chemical formulas 4 to 6, and a second internal electron donor which is selected from the chemical formulas 4 to 6 and is different from the first internal electron donor, and 10 moles of the mixture contains the first internal electron donor and the second internal electron donor in a molar ratio of 3:7 to 7:3.

Description

Ziegler-Natta catalyst for olefin polymerization, method for producing polyolefin, and polyolefin resin

[0001] The present invention relates to a Ziegler-Natta catalyst for olefin polymerization, a method for producing a polyolefin with excellent processability using the same, and a polyolefin resin.

[0002]

[0003] Polyolefins are a class of polymers derived from simple olefins. Known methods for producing polyolefins involve the use of Ziegler-Natta polymerization catalysts. Ziegler-Natta polymerization catalysts use transition metal halides to polymerize vinyl monomers, producing polymers with a highly isotactic stereochemical configuration.

[0004] In particular, as polyethylene, one of the polyolefins, has recently been diversifying its applications, it may be desirable to manufacture polyethylene resin with excellent processability in order to improve resin productivity.

[0005] [Prior Art Literature]

[0006] [Patent Document]

[0007] Republic of Korea Patent Registration No. 10-2423660

[0008]

[0009] The purpose of the present invention is to provide a catalyst for producing a polyolefin having excellent processability by satisfying all of the density, melt index and melt index ratio described in the present specification, and a method for producing a polyolefin having excellent processability.

[0010]

[0011] A Ziegler-Natta catalyst for olefin polymerization is provided.

[0012] According to one embodiment, a Ziegler-Natta catalyst for olefin polymerization comprises a Ziegler-Natta pro-catalyst for olefin polymerization comprising a titanium compound represented by the following chemical formula 1, a magnesium compound represented by the following chemical formula 2, and an internal electron donor; an organoaluminum compound represented by the following chemical formula 7; and an external electron donor represented by the following chemical formula 3, wherein the internal electron donor is a mixture of a first internal electron donor selected from among the following chemical formulas 4 to 6; and a second internal electron donor selected from among the above chemical formulas 4 to 6 and different from the first internal electron donor, wherein in 10 moles of the mixture, the first internal electron donor: the second internal electron donor is contained in a molar ratio of 3:7 to 7:3. In specific examples, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0013] [Chemical Formula 1]

[0014] TiX n (OR 1 ) 4-n

[0015] (In the above chemical formula 1,

[0016] R 1 C1-C substituted or unsubstituted 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0017] X is a halogen atom,

[0018] n is an integer from 0 to 4, and

[0019] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0020] [Chemical Formula 2]

[0021] Mg(OR 2 ) k X 2-k

[0022] (In the above chemical formula 2,

[0023] R 2 C1-C substituted or unsubstituted 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0024] X is a halogen atom,

[0025] k is an integer from 0 to 2, and

[0026] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0027] [Chemical Formula 3]

[0028]

[0029] (In the above chemical formula 3,

[0030] L1 and L2 are each independently substituted or unsubstituted C1-C 20 An alkyl group, and in the above substituted or unsubstituted, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group,

[0031] L3 and L4 are each independently substituted or unsubstituted C1-C 20 Alkyl group and substituted or unsubstituted C3-C 20 One species selected from the group consisting of cycloalkyl groups,

[0032] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0033] [Chemical Formula 4]

[0034]

[0035] (In the above chemical formula 4,

[0036] R 31 , R 32 , R 33 and R 34 are each independently hydrogen, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One selected from the group consisting of aryl groups, or R 31 and R 33 are linked to each other, substituted or unsubstituted C3-C 20 Can form a cycloalkyl group,

[0037] R 4 and R 5 is independently, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0038] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0039] [Chemical Formula 5]

[0040]

[0041] (In the above chemical formula 5,

[0042] R 6 , R 7 and R 8is independently, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0043] n is an integer from 0 to 4, and

[0044] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0045] [Chemical Formula 6]

[0046]

[0047] (In the above chemical formula 6,

[0048] R 9 and R 10 are each independently hydrogen, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One selected from the group consisting of aryl groups, or R 9 and R 10 are connected to each other, substituted or unsubstituted C3-C 20 Can form a cycloalkyl group,

[0049] R 11 and R 12 are each independently substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0050] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0051] [Chemical Formula 7]

[0052] Al(R 13 ) p X 3-p

[0053] (In the above chemical formula 7,

[0054] R 13 Silver hydrogen atom, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0055] X is a halogen atom,

[0056] p is an integer from 0 to 3, and

[0057] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0058] A method for producing polyolefin is provided.

[0059] According to one embodiment, a method for producing a polyolefin comprises a step of polymerizing an olefin monomer in the presence of a Ziegler-Natta catalyst for olefin polymerization.

[0060] A polyolefin resin is provided.

[0061] According to one embodiment, the MFR ratio (MI) is manufactured by the above manufacturing method 21.6 / MI 2.16 ) is about 30.0 to about 50.0. In a specific example, the MFR ratio (MI 21.6 / MI 2.16 ) may be from about 30.5 to about 49.5, for example, from about 30.5 to about 33.5, from about 33.5 to about 36.5, from about 36.5 to about 39.5, from about 39.5 to about 42.5, from about 42.5 to about 45.5, or from about 45.5 to 48.5.

[0062]

[0063] A Ziegler-Natta catalyst for olefin polymerization comprises two types of specific internal electron donors in a specific weight ratio to a specific external electron donor, thereby producing a polyolefin with excellent processability by satisfying all of the density, melt index, and melt index ratio described in the present specification.

[0064]

[0065] The above objectives, other objectives, features, and advantages will be readily understood through the following preferred embodiments, illustrated in the accompanying drawings. However, the embodiments described herein are not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete, and to sufficiently convey the technical concepts to those skilled in the art.

[0066] In describing each drawing, similar reference numerals are used to designate similar components. In the attached drawings, the dimensions of structures are shown exaggerated for clarity of the present invention. Terms such as first, second, etc. may be used to describe various components, but the components should not be limited by these terms. These terms are used only to distinguish one component from another. For example, without departing from the scope of the present invention, a first component could be referred to as a second component, and similarly, a second component could also be referred to as a first component.

[0067] Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0068] In this specification, terms such as “include” or “have” are intended to specify the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but should be understood not to exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0069] Unless otherwise specified, all numbers, values, and / or expressions expressing quantities of ingredients, reaction conditions, polymer compositions, and blends used herein are approximations that inherently reflect, among other things, the various uncertainties of measurement that arise in obtaining such values, and therefore should be understood as being modified in all instances by the term "about." Furthermore, whenever a numerical range is disclosed herein, such range is continuous and includes every value from the minimum value to the maximum value inclusive, unless otherwise indicated. Furthermore, whenever such a range refers to integers, every integer from the minimum value to the maximum value inclusive, unless otherwise indicated, is included.

[0070] In this specification, when a range is described for a variable, the variable will be understood to include all values ​​within the described range including the described endpoints of the range. For example, the range "5 to 10" will be understood to include the values ​​5, 6, 7, 8, 9, and 10, as well as any subranges such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., and any value between integers that fall within the described range, such as 5.5, 6.5, 7.5, 5.5 to 8.5, and 6.5 to 9. Also, for example, a range of "10% to 30%" would be understood to include all integers up to and including 30%, as well as any subranges such as 10% to 15%, 12% to 18%, 20% to 30%, etc., and any value between reasonable integers within the stated range, such as 10.5%, 15.5%, 25.5%, etc.

[0071] Recently, as polyethylene has been diversifying its uses, there has been a need for a catalyst and a method for producing polyethylene resin with excellent processability to improve resin productivity.

[0072] Accordingly, the inventors of the present invention have conducted extensive research to solve the above problem and have provided an olefin-Ziegler-Natta catalyst and a method for producing polyolefin, which produces polyethylene with excellent processability by mixing two types of specific internal electron donors among the main catalysts with a specific molar ratio for a specific external electron donor. Here, "excellent processability" may mean a high melt flow ratio.

[0073] Here, “polyethylene with excellent processability” can be a polyolefin that satisfies the following properties:

[0074] (i) Density: 0.950 to 0.965 g / cm 3

[0075] (ii) Melting index: 0.1 to 10.0 g / 10 min

[0076] (iii) Melt flow ratio: 30.0 to 50.0

[0077] The above density was measured by ASTM D1505.

[0078] The above melt index is the value at a load of 2.16 kg, and was measured at 190°C under a load of 2.16 kg according to ASTM D1238.

[0079] The above melt flow ratio (MFR) is the melt index (MI) at 2.16 kg at 190°C according to ASTM D1238. 2.16 ) and melt index (MI) at 21.6 kg at 190°C according to ASTM D1238 21.6 ) and measure the ratio MI between them 21.6 / MI 2.16 is the calculated value.

[0080] Unless otherwise stated, "C1-C n "Alkyl group" means a linear or branched primary alkyl group having 1 to n carbon atoms, a secondary alkyl group (n ≥ 3), and a tertiary alkyl group (n ≥ 4). For example, it can be a functional group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-hexyl, etc.

[0081] Unless otherwise specified, an aryl group means a chemical group obtained by removing one hydrogen atom from a monocyclic or polycyclic compound having 2 to 30 carbon atoms and a derivative thereof containing one or more benzene rings, and examples of the monocyclic or polycyclic compound containing a benzene ring include a benzene ring, toluene or xylene having an alkyl side chain attached to a benzene ring, biphenyl having two or more benzene rings bonded by a single bond, fluorene, xanthene or anthraquinone having a benzene ring condensed with a cycloalkyl group or a heterocycloalkyl group, naphthalene or anthracene having two or more benzene rings condensed, and the like.

[0082] Unless otherwise specified, the prefix hetero means that one to three heteroatoms selected from the group consisting of -N-, -O-, -S- and -P- replace carbon atoms. For example, it can be pyridine, pyrrole or carbazole containing nitrogen as heteroatom, furan or dibenzofuran containing oxygen as heteroatom, or dibenzothiophene, diphenylamine etc.

[0083] Unless otherwise specified, halogen refers to a group 17 element, such as a fluoro, chloro, bromo or iodo group.

[0084] According to one embodiment, a Ziegler-Natta catalyst for olefin polymerization comprises a main catalyst comprising a titanium compound as described below, a magnesium compound as described below, and an internal electron donor; an organoaluminum as described below; and an external electron donor as described below, wherein two types of internal electron donors as described below are included in a specific molar ratio.

[0085] Specifically, a Ziegler-Natta catalyst for olefin polymerization comprises an external electron donor represented by the following chemical formula 3, and a first internal electron donor and a second internal electron donor selected from the following chemical formulas 4 to 6 and having different chemical structures in a specific molar ratio.

[0086] [External electron donor]

[0087] External electron donors can play a role in stabilizing the catalytically active sites of titanium compounds among the main catalysts. The siloxane-based external electron donor represented by the following chemical formula 3 can facilitate the production of polyolefins with excellent processability when applied to the first internal electron donor and the second internal electron donor described below.

[0088] The external electron donor can be represented by the following chemical formula 3:

[0089] [Chemical Formula 3]

[0090]

[0091] (In the above chemical formula 3,

[0092] L1 and L2 are each independently substituted or unsubstituted C1-C 20 An alkyl group, and in the above substituted or unsubstituted, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group,

[0093] L3 and L4 are each independently substituted or unsubstituted C1-C 20 Alkyl group and substituted or unsubstituted C3-C 20 One selected from the group consisting of cycloalkyl groups, and in the above substituted or unsubstituted, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0094] In one specific embodiment, at least one of L3 and L4 is a substituted or unsubstituted C3-C 20 It may be a cycloalkyl group. In this case, it may be easy to manufacture a polyolefin with excellent processability when applied to the first internal electron donor and the second internal electron donor described below.

[0095] For example, either L3 or L4 is substituted or unsubstituted C3-C20 Cycloalkyl group, for example, substituted or unsubstituted C3-C 10 A cycloalkyl group, which may be a substituted or unsubstituted C5-C6 cycloalkyl group (first external electron donor).

[0096] For example, both L3 and L4 are substituted or unsubstituted C3-C 20 Cycloalkyl group, for example, substituted or unsubstituted C3-C 10 A cycloalkyl group, which may be a substituted or unsubstituted C5-C6 cycloalkyl group (second external electron donor).

[0097] According to one embodiment, the catalyst may include one type of external electron donor represented by the chemical formula 3, i.e., the first external electron donor alone or the second external electron donor alone.

[0098] According to one embodiment, the catalyst may be a mixture comprising two types of external electron donors represented by the above chemical formula 3. In one specific embodiment, the catalyst may be a mixture of the first external electron donor and the second external electron donor. For example, in 10 moles of the mixture, the first external electron donor:the second external electron donor may be included in a molar ratio of about 3:7 to about 7:3, a molar ratio of about 3.5:6.5 to about 6.5:3.5, a molar ratio of about 4:6 to about 6:4, a molar ratio of about 4.5:5.5 to about 5.5:4.5, or a molar ratio of about 5:5.

[0099] In one specific embodiment, L1 and L2 are each independently substituted or unsubstituted C1-C 10 An alkyl group, for example, a substituted or unsubstituted C1-C5 alkyl group.

[0100] In one specific example, the external electron donor may include one or more of the following chemical formulae 3-1 and 3-2:

[0101] [Chemical Formula 3-1]

[0102]

[0103] [Chemical Formula 3-2]

[0104]

[0105] According to one embodiment, the external electron donor may be included in an amount of about 40 wt% to about 60 wt%, based on 100 wt% of the total Ziegler-Natta catalyst for olefin polymerization. In specific examples, the amount may be about 42 wt% to about 58 wt%, for example, about 44 wt% to about 56 wt%, about 46 wt% to about 54 wt%, or about 48 wt% to about 52 wt%. In the above amount range, the stability of the catalyst active site may be high, and there may be no problem of activity reduction due to poisoning of the catalyst active site.

[0106] According to one embodiment, the external electron donor represented by the above chemical formula 3 may be included in an amount of about 95 wt% or more, preferably about 99 wt% to 100 wt%, and more preferably 100 wt%, based on 100 wt% of the total external electron donor contained in the Ziegler-Natta catalyst for olefin polymerization. Within this range, the effect of the present invention may be easily achieved. Here, the 'total external electron donor' may refer to a compound that is independently included compared to the main catalyst in the olefin Ziegler-Natta catalyst, and is known to those skilled in the art to play a role in stabilizing the catalytic active site of the titanium compound.

[0107] [Internal electron donor]

[0108] The internal electron donor is selected so that, when the external electron donor is included in the olefin-Ziegler-Natta catalyst, the polyolefin with excellent processability, i.e., satisfies a specific range of density, melt index, and melt index ratio. The internal electron donor provides various active sites when the external electron donor is applied, thereby enabling the production of a polyolefin resin with excellent processability.

[0109] The internal electron donor is a mixture of a first internal electron donor selected from the following chemical formulae 4 to 6; and a second internal electron donor selected from the above chemical formulae 4 to 6 and different from the first internal electron donor, wherein the first internal electron donor: the second internal electron donor is included in a molar ratio of about 3:7 to about 7:3 in 10 moles of the mixture. In specific examples, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0110] [Chemical Formula 4]

[0111]

[0112] (In the above chemical formula 4,

[0113] R 31 , R 32 , R 33 and R 34 are each independently hydrogen, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One selected from the group consisting of aryl groups, or R 31 and R 33 are linked to each other, substituted or unsubstituted C3-C 20 Can form a cycloalkyl group,

[0114] R 4 and R 5 is independently, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0115] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0116] [Chemical Formula 5]

[0117]

[0118] (In the above chemical formula 5,

[0119] R 6 , R 7 and R 8 is independently, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0120] n is an integer from 0 to 4, and

[0121] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0122] [Chemical Formula 6]

[0123]

[0124] (In the above chemical formula 6,

[0125] R 9 and R 10 are each independently hydrogen, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One selected from the group consisting of aryl groups, or R 9 and R 10 are connected to each other, substituted or unsubstituted C3-C 20 Can form a cycloalkyl group,

[0126] R 11 and R 12are each independently substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0127] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0128] The above mixture includes both a first internal electron donor and a second internal electron donor. An olefin-Ziegler-Natta catalyst comprising only the first internal electron donor and only the second internal electron donor for the external electron donor may have difficulty producing a polyolefin that satisfies all of the above-described density, melt index, and melt index ratio, and in particular, may have difficulty satisfying the above-described melt index ratio, resulting in poor processability.

[0129] The mixture may include both a first internal electron donor and a second internal electron donor, wherein the first internal electron donor: the second internal electron donor may be included in a molar ratio of about 3:7 to about 7:3 among 10 moles of the mixture. In specific examples, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5. At a molar ratio less than about 3:7, for example, about 1:9 or about 2:8, it may be difficult to produce a polyolefin that satisfies all of the above-described density, melt index, and melt index ratio, or the effect of producing a polyolefin with excellent processability due to the addition of the internal electron donor may be weak. At a molar ratio exceeding about 7:3, for example, about 8:2 or about 9:1, it may be difficult to manufacture a polyolefin that satisfies all of the above-described density, melt index, and melt index ratio, or the effect of manufacturing a polyolefin with excellent processability due to the addition of an internal electron donor may be weak.

[0130] In one specific example, the first internal electron donor: the second internal electron donor in the mixture may be included in a molar ratio of about 3:7, about 3.5:6.5, about 4:6, about 4.5:5.5, about 5:5, about 5.5:4.5, about 6:4, about 6.5:3.5, or about 7:3.

[0131] In one specific example, in the chemical formula 4, R 4 and R 5 is independently, a substituted or unsubstituted straight or branched chain, C1-C 20 Alkyl group, for example C1-C 10 It may be an alkyl group, a C1-C5 alkyl group. For example, the compound of the above chemical formula 4 is a diethyl diester compound, and may include at least one of the compounds represented by any one of the chemical formulas 4-1 to 4-7 below:

[0132] [Chemical Formula 4-1]

[0133]

[0134] [Chemical Formula 4-2]

[0135]

[0136] [Chemical Formula 4-3]

[0137]

[0138] [Chemical Formula 4-4]

[0139]

[0140] [Chemical Formula 4-5]

[0141]

[0142] [Chemical Formula 4-6]

[0143]

[0144] [Chemical Formula 4-7]

[0145]

[0146] In one specific example, in the chemical formula 5, R7 and R 8 is independently, substituted or unsubstituted, straight or branched chain, C1-C 20 Alkyl group, e.g. branched chain, C1-C 10 It may be an alkyl group, a branched C1-C5 alkyl group. For example, the compound of the above chemical formula 5 is a diisopropyl diester compound, and may include at least one of the compounds represented by the following chemical formulas 5-1 to 5-2:

[0147] [Chemical Formula 5-1]

[0148]

[0149] [Chemical Formula 5-2]

[0150]

[0151] In one specific example, in the chemical formula 6, R 9 , R 10 , R 11 and R 12 are each independently substituted or unsubstituted, straight or branched, C1-C 20 Alkyl group, for example, straight chain, C1-C 10 An alkyl group may be a straight-chain C1-C5 alkyl group. For example, the compound of the above chemical formula 6 is a diethyl diester compound, and may include at least one of the compounds represented by any one of the chemical formulas 6-1 to 6-4 below:

[0152] [Chemical Formula 6-1]

[0153]

[0154] [Chemical Formula 6-2]

[0155]

[0156] [Chemical Formula 6-3]

[0157]

[0158] [Chemical Formula 6-4]

[0159]

[0160] According to one embodiment, for 1 mole of the external electron donor, the internal electron donor, i.e., the mixture, may be included in an amount of about 0.002 to about 0.008 moles, preferably about 0.003 to about 0.004 moles or about 0.007 to about 0.008 moles. Within this range, polyethylene satisfying the above-described density, melt index, and melt index ratio may be easily produced.

[0161] In one specific example, the mixture is a mixture of the compound of formula 4 and the compound of formula 5, and the compound of formula 4: the compound of formula 5 may be included in a molar ratio of about 3:7 to about 7:3 in 10 moles of the mixture of the compound of formula 4 and the compound of formula 5 (first embodiment). In a specific example, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0162] At this time, in the first embodiment, with respect to 1 mol of the external electron donor, the compound of the chemical formula 4 may be included in an amount of 0.001 to 0.007 mol, preferably 0.003 to 0.004 mol, and the compound of the chemical formula 5 may be included in an amount of 0.001 to 0.007 mol, preferably 0.003 to 0.004 mol. Within the above range, polyethylene with excellent processability may be easily manufactured.

[0163] In one specific embodiment, the mixture is a mixture of the compound of formula 4 and the compound of formula 6, and the compound of formula 4: the compound of formula 6 may be included in a molar ratio of about 3:7 to about 7:3 in 10 moles of the mixture of the compound of formula 4 and the compound of formula 6 (second embodiment). In a specific embodiment, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0164] At this time, in the second embodiment, with respect to 1 mol of the external electron donor, the compound of the chemical formula 4 may be included in an amount of 0.001 to 0.007 mol, preferably 0.003 to 0.004 mol, and the compound of the chemical formula 6 may be included in an amount of 0.001 to 0.007 mol, preferably 0.003 to 0.004 mol. Within the above range, polyethylene with excellent processability may be easily manufactured.

[0165] In one specific embodiment, the mixture is a mixture of the compound of formula 5 and the compound of formula 6, and the compound of formula 5:the compound of formula 6 may be included in a molar ratio of about 3:7 to about 7:3 in 10 moles of the mixture of the compound of formula 5 and the compound of formula 6 (third embodiment). In a specific embodiment, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0166] At this time, in the third embodiment, with respect to 1 mol of the external electron donor, the compound of the chemical formula 5 may be included in an amount of 0.001 to 0.007 mol, preferably 0.003 to 0.004 mol, and the compound of the chemical formula 6 may be included in an amount of 0.001 to 0.007 mol, preferably 0.003 to 0.004 mol. Within the above range, polyethylene with excellent processability may be easily manufactured.

[0167] According to one embodiment, the mixture of the first internal electron donor and the second internal electron donor may be included in an amount of about 95 wt% or more, preferably about 99 wt% to 100 wt%, and more preferably 100 wt%, based on 100 wt% of the total internal electron donor contained in the Ziegler-Natta catalyst for olefin polymerization. Within this range, it is possible to easily produce polyethylene having excellent processability. Here, the 'total internal electron donor' may refer to a compound included in the main catalyst of the olefin Ziegler-Natta catalyst, and is a compound known to those skilled in the art to play a role in stabilizing the catalytic active site of a titanium compound.

[0168] [Titanium compounds]

[0169] The titanium compound may be a compound containing an active center metal, i.e., a metal having an active site. The titanium compound can provide a polyolefin by catalyzing the actual polymerization reaction of an olefinic monomer.

[0170] Titanium compounds are compounds represented by the chemical formula 1 below.

[0171] [Chemical Formula 1]

[0172] TiX n (OR 1 ) 4-n

[0173] (In the above chemical formula 1,

[0174] R 1 C1-C substituted or unsubstituted 20Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0175] X is a halogen atom,

[0176] n is an integer from 0 to 4, and

[0177] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0178] For example, the titanium compound may be at least one selected from the group consisting of tetravalent titanium halides and tetravalent titanium alkoxides. Preferably, the titanium compound may be titanium tetrachloride (TiCl4).

[0179] [magnesium compounds]

[0180] Magnesium compounds can control the properties, such as the activity and stereoregularity of the active center metal having an active site, such as a titanium compound, depending on the molecular structure and bonding strength through bonding with an electron donor as a catalyst support.

[0181] Magnesium compounds are compounds represented by the following chemical formula 2:

[0182] [Chemical Formula 2]

[0183] Mg(OR 2 ) k X 2-k

[0184] (In the above chemical formula 2,

[0185] R 2 C1-C substituted or unsubstituted 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0186] X is a halogen atom,

[0187] k is an integer from 0 to 2, and

[0188] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0189] For example, the magnesium compound may be magnesium dialkoxide, magnesium diaryloxide, or magnesium chloride (MgCl2), and preferably, magnesium diethoxide, which has the advantage of having high purity as magnesium dialkoxide, thereby reducing impurities in the final synthesized catalyst, and being well soluble in a solvent during catalyst synthesis.

[0190] [organic aluminum compounds]

[0191] Organoaluminum compounds can act as cocatalysts to activate the active sites of titanium compounds.

[0192] The organoaluminum compound may include a compound of the following formula 7:

[0193] [Chemical Formula 7]

[0194] Al(R 13 ) p X 3-p

[0195] (In the above chemical formula 7,

[0196] R 13 Silver hydrogen atom, substituted or unsubstituted C1-C 20 Alkyl group, substituted or unsubstituted C3-C 20 Cycloalkyl group, and substituted or unsubstituted C3-C 20 One species selected from the group consisting of aryl groups,

[0197] X is a halogen atom,

[0198] p is an integer from 0 to 3, and

[0199] In the above substitution or non-substitution, the substituent is independently at least one selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group.

[0200] According to one embodiment, the organoaluminum compound may be at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and ethylaluminum dichloride. Preferably, the organoaluminum compound may be triethylaluminum, which can increase polymerization activity and facilitate control of the weight average molecular weight of the polymerized polyolefin.

[0201] [Main catalyst]

[0202] The main catalyst comprises a titanium compound represented by the above chemical formula 1, a magnesium compound represented by the above chemical formula 2, and the internal electron donor, wherein the titanium compound represented by the above chemical formula 1 and the internal electron donor may be supported on a magnesium compound represented by the above chemical formula 2.

[0203] According to one embodiment, the main catalyst may be in a powder state. As described below, a Ziegler-Natta catalyst for olefin polymerization according to one embodiment may be prepared by mixing an organoaluminum compound and an external electron donor with the main catalyst.

[0204] The main catalyst in powder form can be uniformly coated with an organoaluminum compound and an external electron donor. This facilitates the production of a polyolefin having the aforementioned density, melt index, and melt index ratio by ensuring that the main catalyst in powder form is well dispersed within the organoaluminum compound and the external electron donor, thereby enhancing dispersion stability.

[0205] A method for producing a Ziegler-Natta primary catalyst for olefin polymerization may include a first step of mixing a titanium compound represented by Chemical Formula 1 and a magnesium compound represented by Chemical Formula 2 and stirring them; a second step of adding an internal electron donor to the first stirred resultant and stirring them; and a step of vacuum-drying the second stirred resultant.

[0206] The above first stirring step is a step of adding a titanium compound and a magnesium compound to an organic solvent and then stirring at a heating rate of 0.5°C / min to 1.5°C / min from room temperature to the first temperature.

[0207] The organic solvent may be toluene, ether, acetone, alcohol, etc., and preferably, toluene.

[0208] The first temperature may be a temperature of about 70°C to about 90°C, and preferably, a temperature of about 75°C to about 85°C. In specific examples, the first temperature may be about 72°C to about 88°C, for example, about 72°C to about 75°C, about 75°C to about 80°C, about 80°C to about 85°C, or about 85°C to about 88°C. Outside the first temperature range, if the first temperature is too low, there is a disadvantage that the internal electron donor does not dissolve in the solvent, and if the first temperature is too high, there is a disadvantage that a side reaction of the internal electron donor occurs.

[0209] The second stirring step is a step of adding an internal electron donor to the first stirring result, then raising the temperature to a second temperature, and stirring for about 1.8 hours to about 2.2 hours. In specific examples, the stirring time may be about 1.82 hours to about 1.9 hours, about 1.9 hours to about 2 hours, or about 2 hours to about 2.2 hours.

[0210] The second temperature may be about 100°C to about 120°C, and preferably, about 105°C to about 115°C. In specific examples, the second temperature may be about 102°C to about 118°C, for example, about 102°C to about 110°C, about 110°C to about 118°C. Outside the second temperature range, if the second temperature is too low, there is a disadvantage that the titanium compound is not supported on the magnesium compound, and if the second temperature is too high, there is a disadvantage that the solvent evaporates.

[0211] After the second stirring, a third stirring step may be additionally included. Specifically, this is a step of removing the organic solvent and the titanium compound, adding a new organic solvent and the titanium compound, then increasing the temperature from room temperature to the third temperature, and stirring for about 1.8 hours to about 2.2 hours. In specific examples, this may be about 1.82 hours to about 1.9 hours, about 1.9 hours to about 2 hours, or about 2 hours to about 2.2 hours. After stirring, a step of washing the third stirring result using an organic solvent or the like may be further included.

[0212] The third temperature may be about 100°C to about 120°C, and preferably, about 105°C to about 115°C. In specific embodiments, the third temperature may be about 102°C to about 118°C, for example, about 102°C to about 110°C, about 110°C to about 118°C.

[0213] The vacuum drying step is a step of drying the second stirring result or the third stirring result in a vacuum to obtain a Ziegler-Natta main catalyst for olefin polymerization in powder form. At this time, a step of washing the second stirring result or the third stirring result with an organic solvent or the like may be further included before vacuum drying.

[0214] Ziegler-Natta catalyst for olefin polymerization

[0215] The titanium compound and the external electron donor of the Ziegler-Natta primary catalyst for olefin polymerization may be included in a molar ratio of about 1:60 to about 1:380, preferably, about 1:120 to about 1:190. In specific examples, the molar ratio may be about 1:62 to about 1:378, for example, about 1:62 to about 1:150, about 1:150 to about 1:250, or about 1:250 to about 1:378. In the above molar ratio range, the stability of the catalytic active site may be excellent, and there may be no problem of the catalytic activity being reduced due to poisoning of the catalytic active site.

[0216] The organoaluminum compound and external electron donor of the Ziegler-Natta main catalyst for olefin polymerization are about 1:3.0 x 10 -7 About 1:9.0 x 10 -7 , preferably about 1:5.0 x 10 -7 About 1:7.0 x 10 -7 may be included in a molar ratio of about 1:3.2 x 10. In a specific example, the molar ratio is about 1:3.2 x 10 -7 About 1:8.8 x 10 -7 , for example, About 1:3.2 x 10 -7 About 1:5.0 x 10 -7 , approximately 1:5.0 x 10 -7 About 1:7.0 x 10 -7 , Approximately 1:7.0 x 10 -7 About 1:8.8 x 10 -7 It could be. Within the above molar ratio range, it is possible to easily manufacture a polyolefin with excellent processability.

[0217] The magnesium compound and the external electron donor of the Ziegler-Natta primary catalyst for olefin polymerization may be included in a molar ratio of about 1:9 to about 1:13, preferably, about 1:10 to about 1:12. In specific examples, the molar ratio may be 1:9.2 to about 1:12.8, for example, about 1:9.2 to about 1:10.0, about 1:10.0 to about 1:11.0, or about 1:11.0 to about 1:12.8. In the above molar ratio range, it may be easy to produce a polyolefin having excellent processability.

[0218] A method for preparing a Ziegler-Natta catalyst for olefin polymerization includes a step of adding a Ziegler-Natta main catalyst for olefin polymerization, an organoaluminum compound represented by chemical formula 7, and an external electron donor represented by chemical formula 3 to an organic solvent and then stirring the mixture. In this case, among the contents related to the method for preparing a Ziegler-Natta catalyst for olefin polymerization, any contents that overlap with the Ziegler-Natta catalyst for olefin polymerization may be omitted for explanation.

[0219] The organic solvent may be hexane, toluene, ether, acetone, alcohol, etc., and preferably, hexane.

[0220] The stirring speed may be about 280 rpm to about 320 rpm, and preferably, about 290 rpm to about 310 rpm. In specific examples, the stirring speed may be about 285 rpm to about 315 rpm, for example, about 285 rpm to about 295 rpm, about 295 rpm to about 305 rpm, or about 305 rpm to about 315 rpm.

[0221] [Polyolefin manufacturing method]

[0222] According to one embodiment, a method for producing a polyolefin comprises a step of polymerizing an olefin monomer in the presence of a Ziegler-Natta catalyst for olefin polymerization.

[0223] According to one embodiment, the olefinic monomer may include an olefinic monomer having the following chemical formula 8:

[0224] [Chemical Formula 8]

[0225] CH2=CHR 14

[0226] (In the above chemical formula 8,

[0227] R 14 is hydrogen or C1-C6 alkyl or aryl group)

[0228] In one embodiment, the method for producing polyolefin may be a method for producing polyethylene. Accordingly, the method may include a step of introducing and polymerizing an olefin monomer, preferably ethylene, in the presence of a Ziegler-Natta catalyst for olefin polymerization.

[0229] The polyolefin manufacturing method can be polymerized under conditions of a pressure of about 6 bar to about 8 bar and a temperature of about 80°C to about 90°C in a hydrogen gas atmosphere. In addition, if the temperature is too low, the catalyst may not be active, which may result in polymerization failure. If the temperature is too high, the catalyst may overreact, which may result in rapid decrease in activity.

[0230] The polymerization time may be from about 0.5 hours to about 1.5 hours, preferably from about 0.8 hours to about 1.2 hours.

[0231] According to one embodiment, the Ziegler-Natta catalyst for olefin polymerization is about 1.0 x 10 per mole of olefin monomer. -5 About 3.0 x 10 -5 moles, preferably about 1.5 x 10 -5 About 2.5 x 10 -5 It can be included in moles. In a specific example, for 1 mole of the olefin monomer, the Ziegler-Natta catalyst for olefin polymerization is about 1.2 x 10 -5 About 2.9 x 10 -5 moles, for example, about 1.2 x 10 -5About 1.5 x 10 -5 , about 1.5 x 10 -5 About 2 x 10 -5 , About 2 x 10 -5 About 2.5 x 10 -5 , about 2.5 x 10 -5 About 2.9 x 10 -5 It could be. In the above range, the polymerization yield of polyolefin from olefin monomer can be high.

[0232] [Polyolefin resin]

[0233] According to one embodiment, a polyolefin resin is provided. The polyolefin resin is manufactured by the above manufacturing method and has an MFR ratio (MI 21.6 / MI 2.16 ) is about 30.0 to about 50.0. In a specific example, the MFR ratio (MI 21.6 / MI 2.16 ) may be from about 30.5 to about 49.5, for example, from about 30.5 to about 33.5, from about 33.5 to about 36.5, from about 36.5 to about 39.5, from about 39.5 to about 42.5, from about 42.5 to about 45.5, or from about 45.5 to 48.5.

[0234]

[0235] The present invention will be described in more detail below through examples. However, these examples are intended to exemplify the present invention and the scope of the present invention is not limited to these examples.

[0236]

[0237] The specific specifications of the components used in the examples and comparative examples below are as follows:

[0238] External electron donor:

[0239] [Chemical Formula 3-1]

[0240]

[0241] [Chemical Formula 3-2]

[0242]

[0243] Internal electron donor:

[0244] [Chemical Formula 4-1]

[0245]

[0246] [Chemical Formula 5-1]

[0247]

[0248] [Chemical Formula 6-1]

[0249]

[0250]

[0251] Example 1

[0252] Manufacturing Example 1: Manufacturing of Ziegler-Natta main catalyst for olefin polymerization

[0253] 4 g of magnesium compound Mg(OC2H5)2 carrier and 45 ml of titanium compound TiCl were added to 35 ml of toluene, and the temperature was increased from room temperature to 80°C at a heating rate of 1°C / min while stirring at 300 rpm for the first time. Then, when the reaction temperature reached 80°C, 1.4 mmol of chemical formula 4-1 as an internal electron donor and 0.6 mmol of chemical formula 5-1 were added to the first stirred result, and the temperature was increased to 110°C at a heating rate of 1°C, and then maintained for a second stirring for 2 hours. Then, the TiCl4+Toluene solution was removed, and new TiCl4 (13 ml)+toluene (20 ml) was added, and the temperature was increased from room temperature to 100°C at a heating rate of 1°C / min, and maintained for a third stirring for 2 hours. Next, the supported catalyst, which is the third stirring result, was washed four times with 50 ml of toluene at 100°C and twice with 50 ml of hexane at 60°C, and dried in vacuum to obtain a Ziegler-Natta main catalyst (supported catalyst) for olefin polymerization in powder form.

[0254] Manufacturing Example 2: Ziegler-Natta catalyst for olefin polymerization and polyethylene production

[0255] A 2-liter high-pressure reactor was dried in an oven, assembled while hot, and then nitrogen and vacuum were alternately operated three times to create a nitrogen atmosphere inside the reactor. Then, 1000 ml of hexane, an organic solvent, was introduced into the reactor, and 15 mg of a Ziegler-Natta main catalyst for olefin polymerization (Preparation Example 1), 0.24 ml of an external electron donor of chemical formula 3-1 (a solution diluted in hexane at a volume ratio of 1 / 20), and 2 mmol of triethylaluminum (2 ml of a 1 M hexane solution), an organoaluminum compound (cocatalyst), were additionally introduced, and stirred at 300 rpm to prepare a Ziegler-Natta catalyst for olefin polymerization.

[0256] Next, the temperature of the reactor was increased to 85°C, 3 bar of hydrogen was injected once, and then polyethylene polymerization was performed for one hour while continuously adding ethylene at a constant pressure of 7 bar. Next, the temperature of the reactor was lowered to room temperature, and the produced polymer was separated, collected, and dried to obtain a polyethylene polymer in the form of a white powder.

[0257]

[0258] Examples 2 to 27

[0259] In Example 1, a Ziegler-Natta main catalyst for olefin polymerization and a Ziegler-Natta catalyst for olefin polymerization were prepared and polyethylene was prepared in the same manner as in Example 1, except that the internal electron donor and external electron donor were changed as shown in Table 1 below.

[0260]

[0261] Comparative Example 1

[0262] Manufacturing Example 1: Manufacturing of Ziegler-Natta main catalyst for olefin polymerization

[0263] 4 g of magnesium compound Mg(OC2H5)2 carrier and 45 ml of titanium compound TiCl were added to 35 ml of toluene, and the temperature was increased from room temperature to 80°C at a heating rate of 1°C / min while stirring at 300 rpm for the first time. Then, when the reaction temperature reached 80°C, 2.0 mmol of chemical formula 4-1, which is an internal electron donor, was added to the first stirred result, and the temperature was increased to 110°C at a heating rate of 1°C, and then maintained for a second stirring for 2 hours. Then, the TiCl4+Toluene solution was removed, and new TiCl4 (13 ml)+toluene (20 ml) was added, and the temperature was increased from room temperature to 100°C at a heating rate of 1°C / min, and maintained for a third stirring for 2 hours. Next, the supported catalyst, which is the third stirring result, was washed four times with 50 ml of toluene at 100°C and twice with 50 ml of hexane at 60°C, and dried in vacuum to obtain a Ziegler-Natta main catalyst (supported catalyst) for olefin polymerization in powder form.

[0264] Manufacturing Example 2: Ziegler-Natta catalyst for olefin polymerization and polyethylene production

[0265] A 2-liter high-pressure reactor was dried in an oven, assembled while hot, and then nitrogen and vacuum were alternately operated three times to create a nitrogen atmosphere inside the reactor. Then, 1000 ml of hexane, an organic solvent, was introduced into the reactor, and 15 mg of a Ziegler-Natta main catalyst for olefin polymerization (Preparation Example 1), 0.24 ml of chemical formula 3-1, an external electron donor (a solution diluted in hexane at a volume ratio of 1 / 20), and 2 mmol of triethylaluminum, an organoaluminum compound (cocatalyst) (2 ml of a 1 M hexane solution), were additionally introduced, and stirred at 300 rpm to prepare a Ziegler-Natta catalyst for olefin polymerization.

[0266] Then, after the temperature of the reactor was raised to 85℃, 3 bar of hydrogen was injected once, and then, ethylene pressure was continuously increased to a constant pressure of 7 bar (2.0 x 10 Ziegler-Natta catalyst for olefin polymerization per mole of ethylene -5 Polyethylene polymerization was performed for one hour while adding (injected into the mole) the temperature of the reactor was lowered to room temperature, and the produced polymer was separated, collected, and dried to obtain a polyethylene polymer in the form of a white powder.

[0267]

[0268] Comparative Examples 2 to 15

[0269] In Comparative Example 1, a Ziegler-Natta main catalyst for olefin polymerization and a Ziegler-Natta catalyst for olefin polymerization were prepared and polyethylene was prepared in the same manner as in Comparative Example 1, except that the internal electron donor and external electron donor were changed as shown in Table 1 below.

[0270]

[0271] Polyethylene property evaluation method

[0272] Active (G PE / Gcat)(Unit: None): Obtained resin weight (g) / catalyst weight (g)

[0273] MI 2.16 (Unit: g / 10min) and MI 21.6 (Unit: g / 10min): Using TOYOSEIKI MELT INDEXER P-101 measuring device, according to ASTM D 1238, load (MI) of 2.16 kg at 190℃ 2.16 ) and a load of 21.6 kg (MI 21.6 ) measured

[0274] Melt Flow Ratio: Melt Index MI 21.6 and MI 2.16 Each is measured according to ASTM D 1238 and the ratio is MFR = (MI 21.6 / MI 2.16 ) to find

[0275] Density (unit: g / cm) 3 ): Measured according to ASTM D1505

[0276] Internal electron donor External electron donor Activity MI (I 2.16 )MI (I 21.6) MFR density Example 1 Chemical formula 4-1 + Chemical formula 5-1 (7:3 molar ratio) Chemical formula 3-13,8261.044.144.10.954 Example 2 Chemical formula 4-1 + Chemical formula 5-1 (7:3 molar ratio) Chemical formula 3-23,1600.834.042.50.955 Example 3 Chemical formula 4-1 + Chemical formula 5-1 (7:3 molar ratio) Chemical formula 3-1 + Chemical formula 3-23,7160.14.848.40.964 Example 4 Chemical formula 4-1 + Chemical formula 5-1 (5:5 molar ratio) Chemical formula 3-14,1600.836.645.80.956 Example 5 Chemical formula 4-1 + Chemical formula 5-1 (5:5 molar ratio) Chemical formula 3-24,3940.28.643.20.955Example 6Chemical formula 4-1 + chemical formula 5-1 (5:5 molar ratio)Chemical formula 3-1 + chemical formula 3-23,7952.2104.547.50.956Example 7Chemical formula 4-1 + chemical formula 5-1 (3:7 molar ratio)Chemical formula 3-15,1651.342.132.40.957Example 8Chemical formula 4-1 + chemical formula 5-1 (3:7 molar ratio)Chemical formula 3-23,5335.7184.732.40.962Example 9Chemical formula 4-1 + chemical formula 5-1 (3:7 molar ratio)Chemical formula 3-1 + chemical formula 3-25,0550.620.534.20.961Example 10Chemical formula 4-1 + Chemical formula 6-1 (7:3 molar ratio) Chemical formula 3-13,2670.726.037.20.957 Example 11 Chemical formula 4-1 + Chemical formula 6-1 (7:3 molar ratio) Chemical formula 3-24,6671.140.737.00.961 Example 12 Chemical formula 4-1 + Chemical formula 6-1 (7:3 molar ratio) Chemical formula 3-1 + Chemical formula 3-23,2790.625.342.20.955 Example 13 Chemical formula 4-1 + Chemical formula 6-1 (5:5 molar ratio) Chemical formula 3-14,9330.13.939.40.957 Example 14 Chemical formula 4-1 + Chemical formula 6-1 (5:5 molar ratio) Chemical formula 3-24,6002.474.230.90.961Example 15Chemical formula 4-1 + chemical formula 6-1 (5:5 molar ratio)Chemical formula 3-1 + chemical formula 3-24,4790.519.739.30.957Example 16Chemical formula 4-1 + chemical formula 6-1 (3:7 molar ratio)Chemical formula 3-14,6670.13.736.90.952Example 17Chemical formula 4-1 + chemical formula 6-1 (3:7 molar ratio)Chemical formula 3-23,9782.797.736.20.958Example 18Chemical formula 4-1 + chemical formula 6-1 (3:7 molar ratio)Chemical formula 3-1 + chemical formula 3-24,0242.175.435.90.958Example 19Chemical formula 6-1 + chemical formula 5-1 (7:3 molar ratio)Chemical formula 3-15,8167.3241.633.10.962Example 20Chemical formula 6-1 + chemical formula 5-1 (7:3 molar ratio)Chemical formula 3-26,2563.6115.932.20.964Example 21Chemical formula 6-1 + chemical formula 5-1 (7:3 Molar ratio) Chemical formula 3-1 + Chemical formula 3-26,1341.652.032.50.964Example 22 Chemical formula 6-1 + Chemical formula 5-1 (5:5 molar ratio) Chemical formula 3-16,7330.515.731.40.957Example 23 Chemical formula 6-1 + Chemical formula 5-1 (5:5 molar ratio) Chemical formula 3-25,8670.619.131.80.956Example 24 Chemical formula 6-1 + Chemical formula 5-1 (5:5 molar ratio) Chemical formula 3-1 + Chemical formula 3-26,2670.515.230.30.964Example 25 Chemical formula 6-1 + Chemical formula 5-1 (3:7 molar ratio) Chemical formula 3-15,2671.032.232.20.960Example 26Chemical formula 6-1 + chemical formula 5-1 (3:7 molar ratio)Chemical formula 3-25,2671.237.831.50.960Example 27Chemical formula 6-1 + chemical formula 5-1 (3:7 molar ratio)Chemical formula 3-1 + chemical formula 3-25,4670.13.534.70.958Comparative example 1Chemical formula 4-1Chemical formula 3-14,6001.336.127.80.961Comparative example 2Chemical formula 4-1Chemical formula 3-24,5331.336.828.30.962Comparative example 3Chemical formula 4-1Chemical formula 3-1 + chemical formula 3-25,6671.132.029.10.957Comparative Example 4 Chemical Formula 5-1 Chemical Formula 3-16,6670.719.127.30.954Comparative Example 5 Chemical Formula 5-1 Chemical Formula 3-26,2671.434.424.60.960Comparative Example 6 Chemical Formula 5-1 Chemical Formula 3-1+ Chemical Formula 3-25,6001.641.025.60.956Comparative Example 7 Chemical Formula 6-1 Chemical Formula 3-16,1676.1162.326.60.959Comparative Example 8Chemical Formula 6-1Chemical Formula 3-25,6005.0125.025.00.957Comparative Example 9Chemical Formula 6-1Chemical Formula 3-1 + Chemical Formula 3-25,0672.564.025.60.959Comparative Example 10Chemical Formula 4-1 + Chemical Formula 5-1 (8:2 molar ratio)Chemical Formula 3-14,2500.823.829.80.958Comparative Example 11Chemical Formula 4-1 + Chemical Formula 5-1 (2:8 molar ratio)Chemical Formula 3-15,2371.538.925.90.956Comparative Example 12Chemical Formula 4-1 + Chemical Formula 6-1 (8:2 molar ratio)Chemical Formula 3-16,1576.9191.827.80.956Comparative Example 13Chemical Formula 4-1 + Chemical Formula 6-1 (2:8 molar ratio)Chemical Formula 3-15,5331.334.526.50.959Comparative Example 14Chemical Formula 6-1 + Chemical Formula 5-1 (8:2 molar ratio)Chemical Formula 3-16,9504.6111.824.30.962Comparative Example 15Chemical Formula 6-1 + Chemical Formula 5-1 (2:8 molar ratio)Chemical Formula 3-15,8602.565.526.20.962.

[0277]

[0278] *In Table 1 above,

[0279] The total moles of internal electron donors are 0.0038 mmol

[0280] The total moles of external electron donors are 1.2 mmol

[0281] Among the external electron donors, the molar ratio of Chemical Formula 3-1: Chemical Formula 3-2 in Chemical Formula 3-1 + Chemical Formula 3-2 is 1:1.

[0282]

[0283] Referring to Table 1 above, the Ziegler-Natta catalyst for olefin polymerization of the example produced a polyolefin that simultaneously satisfies the original density, melt index, and melt index ratio.

[0284] On the other hand, the Ziegler-Natta catalyst for olefin polymerization that does not satisfy the original composition could not produce a polyolefin that simultaneously satisfies the original density, melt index, and melt index ratio.

[0285]

[0286] Simple modifications or changes of the present invention can be easily implemented by a person having ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

[0287]

[0288] A Ziegler-Natta catalyst for olefin polymerization comprises two types of specific internal electron donors in a specific weight ratio to a specific external electron donor, thereby producing a polyolefin with excellent processability by satisfying all of the density, melt index, and melt index ratio described in the present specification.

Claims

1. A Ziegler-Nattaju catalyst for olefin polymerization comprising a titanium compound represented by the following chemical formula 1, a magnesium compound represented by the following chemical formula 2, and an internal electron donor; An organoaluminum compound represented by the following chemical formula 7; and Contains an external electron donor represented by the following chemical formula 3; The internal electron donor is a mixture of a first internal electron donor selected from the following chemical formulae 4 to 6; and a second internal electron donor selected from the above chemical formulae 4 to 6 and different from the first internal electron donor. A Ziegler-Natta catalyst for olefin polymerization, wherein the first internal electron donor: the second internal electron donor are included in a molar ratio of 3:7 to 7:3 among 10 moles of the above mixture: [Chemical Formula 1] TiX n (OR 1 ) 4-n (In the above chemical formula 1, R 1 C is substituted or unsubstituted 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, X is a halogen atom, n is an integer from 0 to 4, and In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 At least one selected from the group consisting of alkyl groups) [Chemical formula 2] Mg(OR 2 ) k X 2-k (In the above chemical formula 2, R 2 C is substituted or unsubstituted 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, X is a halogen atom, k is an integer from 0 to 2, and In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 At least one selected from the group consisting of alkyl groups) [Chemical Formula 3] (In the above chemical formula 3, L 1 and L 2 are each independently substituted or unsubstituted C 1 -C 20 It is an alkyl group, In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 At least one selected from the group consisting of alkyl groups, L 3 and L 4 are each independently substituted or unsubstituted C 1 -C 20 Alkyl group and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of cycloalkyl groups, In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 (At least one selected from the group consisting of alkyl groups). [Chemical Formula 4] (In the above chemical formula 4, R 31 , R 32 , R 33 and R 34 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, or R 31 and R 33 are connected to each other, substituted or unsubstituted C 3 -C 20 can form a cycloalkyl group, R 4 and R 5 is independently, substituted or unsubstituted C 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 At least one selected from the group consisting of alkyl groups) [Chemical Formula 5] (In the above chemical formula 5, R 6 , R 7 and R 8 is independently, substituted or unsubstituted C 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, n is an integer from 0 to 4, and In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 At least one selected from the group consisting of alkyl groups) [Chemical formula 6] (In the above chemical formula 6, R 9 and R 10 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, or R 9 and R 10 are connected to each other, substituted or unsubstituted C 3 -C 20 can form a cycloalkyl group, R 11 and R 12 are each independently substituted or unsubstituted C 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 At least one selected from the group consisting of alkyl groups) [Chemical formula 7] Al(R 13 ) p X 3-p (In the above chemical formula 7, R 13 C is a hydrogen atom, substituted or unsubstituted. 1 -C 20 C, alkyl group, substituted or unsubstituted 3 -C 20 Cycloalkyl group, and substituted or unsubstituted C 3 -C 20 One selected from the group consisting of aryl groups, X is a halogen atom, p is an integer from 0 to 3, and In the above substitution or non-substitution, the substituents are independently a halogen group, a cyano group, a nitro group, and C 1 -C 8 (At least one selected from the group consisting of alkyl groups).

2. A Ziegler-Natta catalyst for olefin polymerization, wherein in the first paragraph, the mixture is a mixture of the compound of the chemical formula 4 and the compound of the chemical formula 5, and the compound of the chemical formula 4: the compound of the chemical formula 5 is contained in a molar ratio of 3:7 to 7:3 among 10 mol of the mixture of the compound of the chemical formula 4 and the compound of the chemical formula 5.

3. A Ziegler-Natta catalyst for olefin polymerization, wherein in the first paragraph, the mixture is a mixture of the compound of the chemical formula 4 and the compound of the chemical formula 6, and the compound of the chemical formula 4: the compound of the chemical formula 6 is contained in a molar ratio of 3:7 to 7:3 among 10 mol of the mixture of the compound of the chemical formula 4 and the compound of the chemical formula 6.

4. A Ziegler-Natta catalyst for olefin polymerization, wherein in the first paragraph, the mixture is a mixture of the compound of the chemical formula 5 and the compound of the chemical formula 6, and the compound of the chemical formula 5: the compound of the chemical formula 6 is contained in a molar ratio of 3:7 to 7:3 among 10 mol of the mixture of the compound of the chemical formula 5 and the compound of the chemical formula 6.

5. In paragraph 1, the compound of formula 4 includes at least one of the compounds represented by any one of the following formulas 4-1 to 4-7, the compound of formula 5 includes at least one of the compounds represented by any one of the following formulas 5-1 or 5-2, and the compound of formula 6 includes at least one of the compounds represented by any one of the following formulas 6-1 to 6-4, a Ziegler-Natta catalyst for olefin polymerization: [Chemical Formula 4-1] [Chemical Formula 4-2] [Chemical Formula 4-3] [Chemical Formula 4-4] [Chemical Formula 4-5] [Chemical Formula 4-6] [Chemical Formula 4-7] [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 6-1] [Chemical Formula 6-2] [Chemical Formula 6-3] [Chemical Formula 6-4] 6. A Ziegler-Natta catalyst for olefin polymerization, wherein the internal electron donor is contained in an amount of 0.002 to 0.008 moles per 1 mole of the external electron donor in the first paragraph.

7. In the first paragraph, the external electron donor is L in the chemical formula 3. 3 and L 4 At least one of them is substituted or unsubstituted C 3 -C 20 A Ziegler-Natta catalyst for olefin polymerization, which is a cycloalkyl group.

8. In the 7th paragraph, the external electron donor is L in the chemical formula 3. 3 and L 4 Either C is substituted or unsubstituted. 3 -C 20 A first external electron donor, which is a cycloalkyl group, and L in the chemical formula 3 3 and L 4 All are substituted or unsubstituted C 3 -C 20 A Ziegler-Natta catalyst for olefin polymerization, comprising a mixture of a second external electron donor and a cycloalkyl group.

9. A Ziegler-Natta catalyst for olefin polymerization, wherein in the 8th paragraph, the first external electron donor: the second external electron donor are included in a molar ratio of 3:7 to 7:3 among 10 moles of the mixture.

10. In the 7th paragraph, the external electron donor is a Ziegler-Natta catalyst for olefin polymerization, comprising at least one of the following chemical formulas 3-1 and 3-2: [Chemical Formula 3-1] [Chemical Formula 3-2] 11. A Ziegler-Natta catalyst for olefin polymerization, wherein the external electron donor is included in an amount of 40 to 60 wt% based on 100 wt% of the Ziegler-Natta catalyst for olefin polymerization.

12. A Ziegler-Natta catalyst for olefin polymerization, wherein the mixture of the first internal electron donor and the second internal electron donor is comprised in an amount of 95 wt% or more based on 100 wt% of the total internal electron donor contained in the Ziegler-Natta catalyst for olefin polymerization.

13. A method for producing a polyolefin, comprising a step of polymerizing an olefin monomer in the presence of a Ziegler-Natta catalyst for olefin polymerization according to any one of claims 1 to 12.

14. In the 13th paragraph, the Ziegler-Natta catalyst for olefin polymerization is 1.0 x 10 for 1 mole of the olefin monomer. -5 3.0 x 10 -5 A method for producing polyolefin, comprising:

15. Manufactured by the manufacturing method of Article 13, and having an MFR ratio (MI) 21.6 / MI 2.16 ) is 30.0 to 50.0, characterized in that the polyolefin resin.

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